Aqueous compositions

ABSTRACT

The invention relates to novel aqueous compositions containing (1) organosilicon compounds comprising ammonium groups, containing at least one grouping consisting of two protonated nitrogen atoms per molecule, said atoms being linked by at least three carbon atoms, (2) acid anions, the corresponding acids thereof having a pk a  value higher than 0, (3) water, (4) optionally a solvent which can be mixed with water, and (5) optionally emulsifying agents. Said aqueous compositions are preferably homogeneous aqueous solutions.

[0001] This invention relates to aqueous compositions comprisingorganosilicon compounds.

[0002] U.S. Pat. No. 4,101,272 (Commonwealth Scientific and IndustrialResearch Organization, issued Jul. 18, 1978) describes a process for thetreatment of wool that comprises epoxysiloxanes and amines being appliedto the wool as separate substances and reacting in situ to formcrosslinked insoluble structures.

[0003] U.S. Pat. No. 4,833,225 (Goldschmidt, issued May 23, 1989)discloses polyquaternary polysiloxane polymers of the block structure(AB)_(n)A, which are obtained by reaction of α,ω-epoxysiloxanes withditertiary diamines in the presence of acids. The block copolymerscontain quaternary nitrogen atoms.

[0004] U.S. Pat. No. 5,807,956 (OSi Specialties, Inc., issued Sep. 15,1998) describes block copolymers of the structure (AB)_(n)A whichcontain polyalkylene oxide chains. They are prepared by reactingα,ω-epoxysiloxanes with α,ω-aminoalkyl polyethers, although the poormutual solubility of the reactants means that relatively large amountsof organic solvents are needed to achieve adequate compatibility.

[0005] U.S. Pat. No. 6,001,422 (Shin-Etsu Chemical Co., issued Dec. 14,1999) discloses aminoalkyl-containing diorganopolysiloxanes and theiruse in aqueous formulations whose basic nitrogen atoms are separated by—CH₂—CH₂-groups. The aminosiloxanes described have amine equivalentvalues from 5 000 to 100 000 g/mol, corresponding to an amine nitrogencontent from 0.014 to 0.28% by weight.

[0006] It is an object of the present invention to provide aqueouscompositions of organosilicon compounds which contain organic radicalscontaining basic nitrogen and which are soluble or self-dispersing inwater in particular and, in particular, have a lower basic nitrogencontent than hitherto. This object is achieved by the invention.

[0007] The present invention accordingly provides aqueous compositionscontaining

[0008] (1) ammonio-containing organosilicon compounds which, permolecule, contain at least one moiety of two protonated nitrogen atomsjoined together through at least three carbon atoms,

[0009] (2) acid anions whose corresponding acids have a pk_(a) value ofgreater than 0, preferably greater than 2 and more preferably greaterthan 3,

[0010] (3) water,

[0011] optionally

[0012] (4) water-miscible solvents

[0013] and optionally

[0014] (5) emulsifiers.

[0015] The aqueous compositions are preferably homogeneous aqueoussolutions, aqueous microemulsions and aqueous emulsions, of whichhomogeneous aqueous solutions are preferred.

[0016] The aqueous compositions according to the present invention areprepared by mixing the inventive (1) ammonio-containing organosiliconcompounds together with their (2) acid anions with (3) water, optionally(4) water-miscible solvents and optionally (5) emulsifiers.

[0017] The inventive (1) ammonio-containing organosilicon compoundstogether with their (2) acid anions are preferably obtained by reactingthe amino-containing organosilicon compounds corresponding to (1) withacids corresponding to (2).

[0018] The use of (5) emulsifiers is not preferred.

[0019] The inventive (1) ammonio-containing organosilicon compoundspreferably contain at least one moiety of the general formula

[0020] where z is an integer from 1 to 20.

[0021] Preferred inventive ammonio-containing organosilicon compoundscontain

[0022] (a) at least one structural unit Y of the general formula

[0023] where R² is a divalent organic radical,

[0024] R³ is a hydrogen atom or a monovalent hydrocarbon radical having1 to 60 carbon atoms per radical which may be interrupted or substitutedby one or more separate hetero atoms selected from the group consistingof nitrogen, oxygen, sulfur and halogen,

[0025] R^(3′) has the meaning of R³, preferably a hydrogen atom or amonovalent hydrocarbon radical having 1 to 12 carbon atoms per radical,

[0026] R⁴ is a divalent hydrocarbon radical having 1 to 10 carbon atomsper radical, preferably 3 to 10 carbon atoms per radical,

[0027] n is 0 or an integer from 1 to 10,

[0028] m is an integer from 2 to the total number of nitrogen atoms in(I), preferably an integer from 2 to the sum formed from n+1 and thetotal number of any basic nitrogen atoms contained in the R³ radicals,and

[0029] each x is the same or different and represents 0 or 1,

[0030] X⁻ is an acid anion whose corresponding acid has a pK_(a) valuegreater than 0, preferably greater than 2, more preferably greater than3, with the proviso that the structural unit of formula (I) contains atleast one moiety of two protonated nitrogen atoms which are joinedtogether through at least three carbon atoms,

[0031] and

[0032] (b) at least one siloxane unit of the general formula

[0033] where each R is the same or different and represents a monovalentoptionally halogenated hydrocarbon radical having 1 to 18 carbon atomsper radical,

[0034] each R¹ is the same or different and represents a monovalenthydrocarbon radical having 1 to 8 carbon atoms per radical,

[0035] a is 0, 1, 2 or 3,

[0036] b is 0, 1, 2 or 3,

[0037] with the proviso that the sum of a+b is ≦3,

[0038] and

[0039] (c) at least one siloxane unit of the general formula

[0040] where R, R¹, a and b are each as defined above,

[0041] with the proviso that the sum of a+b is ≦2 and

[0042] that the siloxane unit of the formula (III) is bonded through thesilicon atoms to the structural unit of the formula (I) through the R²radicals,

[0043] and optionally

[0044] (d) at least one structural unit Y′ of the general formula

[0045] where R², R³, R⁴, n, m x and X⁻ are each as defined above,

[0046] with the proviso that the structural unit of the formula (I′)contains at least one moiety of two protonated nitrogen atoms which arejoined together through at least three carbon atoms, and

[0047] (e) at least two siloxane units of the general formula

[0048] where R, R¹, a and b are each as defined above,

[0049] with the proviso that the sum of a+b is ≦2 and

[0050] that the siloxane units of the formula (III′) are joined throughthe silicon atoms to the structural unit of the formula (I′) through theR² radicals.

[0051] Preferred inventive ammonio-containing organosilicon compoundscontain

[0052] (a′) at least one siloxane unit of the general formula

[0053] where Y is an organic radical of formula (I) and

[0054] R, R¹, a and b are each as defined above,

[0055] with the proviso that the sum of a+b is ≦2,

[0056] (b) at least one siloxane unit of the general formula

[0057] where R, R¹, a and b are each as defined above,

[0058] with the proviso that the sum of a+b is ≦3,

[0059] and optionally

[0060] (d′) at least one bridge unit of the general formula

[0061] where Y′ is an organic radical of the formula (I′) and

[0062] R, R¹, a and b are each as defined above,

[0063] with the proviso that the sum of a+b is ≦2.

[0064] The ammonium nitrogen content is preferably from 0.3 to 5.0% byweight and more preferably from 0.5 to 5.0% by weight, each percentagebeing based on the total weight of the ammonio-containing organosiliconcompounds.

[0065] The viscosity of the inventive ammonio-containing organosiliconcompounds is preferably 50-5 000 000 mPa.s at 25° C. and more preferably100-100 000 mPa.s at 25° C.

[0066] The inventive ammonio-containing organosilicon compounds arepreparable by reaction of (poly)amines with epoxy-containingorganosilicon compounds.

[0067] When the (poly)amine contains just one nitrogen-attached hydrogenatom, a monoaddition takes place.

[0068] The monoaddition of (poly)amines having an N-attached hydrogenatom to epoxy-containing organosilicon compounds is known and describedfor example in U.S. Pat. No. 3,389,160 (Union Carbide Corporation).

[0069] When the (poly)amine contains at least two nitrogen-attachedhydrogen atoms, a polyaddition takes place.

[0070] The nitrogen atoms are then protonated by reaction with acids.

[0071] When the inventive ammonio-containing organosilicon compounds areprepared by the abovementioned polyaddition, they will contain the units(d) and (e), ie the bridge units (d′), in addition to the units (a), (b)and (c) or (a′) and (b) as the case may be.

[0072] Useful inventive ammonio-containing organosilicon compounds arefurther prepared by reaction of chloroalkylalkoxysilanes, such aschloroalkyldimethoxymethylsilanes, with (poly)amines, such ashexamethylenediamine, and equilibration of the resultantaminoalkylalkoxysilanes, such as aminoalkyldimethoxymethylsilanes, ortheir hydrolysis and/or condensation products, with organopolysiloxanes,such as linear triorganosiloxy-terminated organopolysiloxanes, linearhydroxyl-terminated organopolysiloxanes, cyclic organopolysiloxanes orcopolymers of diorganosiloxane and monoorganosiloxane units.

[0073] The nitrogen atoms are then protonated by reaction with acids.

[0074] Such amino-functional organosilicon compounds and also theirpreparation are known and described for example in U.S. Pat. No.2,971,864 (Dow Corning Corporation, issued Feb. 14, 1961) and J. L.Speier et al., J. ORG. CHEM. 36, 3120 (1971).

[0075] Examples of R radicals are alkyl radicals, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,neopentyl, tert-pentyl, hexyl, such as n-hexyl, heptyl, such asn-heptyl, octyl, such as n-octyl and isooctyl, such as2,2,4-trimethylpentyl, nonyl, such as n-nonyl, decyl, such as n-decyl,dodecyl, such as n-dodecyl, and octadecyl, such as n-octadecyl,cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl andmethylcyclohexyl, aryl, such as phenyl, naphthyl, anthryl andphenanthryl, alkaryl, such as o-, m-, p-tolyl, xylyl and ethylphenyl,and aralkyl, such as benzyl, α-phenylethyl and β-phenylethyl.

[0076] Examples of substituted R radicals are haloalkyl, such as3,3,3-trifluoro-n-propyl, 2,2,2,2′,2′,2′-hexafluoroisopropyl,heptafluoroisopropyl and haloaryl, such as o-, m- and p-chlorophenyl.

[0077] R is preferably methyl.

[0078] Examples of R¹ radicals are alkyl, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,neopentyl, tert-pentyl, hexyl, such as n-hexyl, heptyl, such asn-heptyl, octyl, such as n-octyl and isooctyl, such as2,2,4-trimethylpentyl.

[0079] R² is preferably an organic radical selected from the group

(Si)—(R⁵)_(t)—CR⁶(OH)—CR⁶ ₂—(N)   (VI),

[0080] and

[0081] a divalent hydrocarbon radical having 1 to 10 carbon atoms perradical,

[0082] where (Si)— is the bond to the silicon atom of the siloxane unitof the formula (IV) or (V) as the case may be and —(N) is the bond tothe nitrogen atom of the structural unit Y or Y′ of the formula (I) or(I′) as the case may be,

[0083] R⁵ is a divalent hydrocarbon radical having 1 to 10 carbon atomsper molecule which may be substituted by an ether oxygen atom,

[0084] R⁶ is a hydrogen atom or a monovalent hydrocarbon radical having1 to 10 carbon atoms per radical which may be substituted by an etheroxygen atom,

[0085] R⁷ is a trivalent hydrocarbon radical having 3 to 12 carbon atomsper radical and

[0086] t is 0 or 1.

[0087] Examples of R² radicals are aliphatic, cycloaliphatic andaromatics-containing divalent organic radicals which contain hydroxylfunctions from the epoxide ring opening such as

[0088] where r is an integer from 1 to 20 and preferably from 2 to 8,and —(N) is the bond to the nitrogen atom of the structural unit Y ofthe formula (I)

[0089] and alkylene radicals, such as

—(CH₂)—

—(CH₂)₂—

—(CH₂)₃—

—CH₂CH(CH₃)CH₂—

—(CH₂CH₂CH(CH₃)—

—(CH₂)₄—

—(CH₂)₆—

[0090] Preferred R² radicals are

[0091] and the first two radicals and the —(CH₂)₃— radical areparticularly preferred.

[0092] Examples of R³ hydrocarbon radicals are alkyl radicals, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, such as n-hexyl,heptyl, such as n-heptyl, octyl, such as n-octyl and isooctyl, such as2,2,4-trimethylpentyl, nonyl, such as n-nonyl, decyl, such as n-decyl,dodecyl, such as n-dodecyl, and octadecyl, such as n-octadecyl,cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl andmethylcyclohexyl, aryl, such as phenyl, naphthyl, anthryl andphenanthryl, alkaryl, such as o-, m-, p-tolyl, xylyl and ethylphenyl,and aralkyl, such as benzyl, α-phenylethyl and β-phenylethyl.

[0093] Examples of R³ halogenated radicals are haloalkyl, such as3,3,3-trifluoro-n-propyl, 2,2,2,2′,2′,2′-hexafluoroisopropyl,heptafluoroisopropyl and haloaryl, such as o-, m- and p-chlorophenyl.

[0094] Examples of R³ radicals substituted by a nitrogen atom are as thecase may be

—C₂H₄NEt₂ or —C₂H₄N⁺HEt₂ * X⁻

—C₂H₄NMe₂ or —C₂H₄N⁺HMe₂ * X⁻

—C₃H₆NMe₂ or —C₃H₆N⁺HMe₂ * X⁻

—C₃H₆NEt₂ or —C₃H₆N⁺HEt₂ * X⁻

—C₄H₈NMe₂ or —C₄H₈N⁺HMe₂ * X⁻

—C₂H₄NMeC₂H₄NMe₂ or —C₂H₄N⁺HMeC₂H₄N⁺HMe₂ * 2X⁻

—C₃H₆NEtC₃H₆NEt₂ or —C₃H₆N⁺HEtC₃H₆N⁺HEt₂ * 2X⁻

[0095] where Me is methyl and Et is ethyl.

[0096] Examples of R³ radicals substituted by an oxygen atom are

—(C₂H₄O)_(s)R

—(C₃H₆O)_(s)R,

—(C₂H₄O)_(s)(C₃H₆O)_(s)R

[0097] and

—(C₄H₈O)_(s)R,

[0098] where s is an integer from 1 to 30, preferably from 1 to 20 and Ris as defined above, preferably is methyl or butyl.

[0099] Examples of R³ radicals which are substituted by a nitrogen atomand an oxygen atom are as the case may be

—(C₂H₄O)_(s)C₃H₆NR¹ ₂ or —(C₂H₄O)_(s)C₃H₆N⁺HR¹ ₂ * X⁻

—(C₃H₆O)_(s)C₃H₆NR¹ ₂ or —(C₃H₆O)_(s)C₃H₆N⁺HR¹ ₂ * X⁻

[0100] and

—(C₂H₄O)_(s)(C₃H₆O)_(S)C₃H₆NR¹ ₂ or —(C₂H₄O)_(s)(C₃H₆O)_(s)C₃H₆N⁺HR¹ ₂ *X⁻,

[0101] where s, R¹ and X⁻ are each as defined above and R¹ is preferablymethyl or ethyl.

[0102] Examples of R³ radicals substituted by a sulfur atom are

—(C²H⁴S)_(s)R and

—(C³H⁶S)_(s)R,

[0103] where s and R are each as defined above and R is preferablymethyl, ethyl or butyl.

[0104] Examples of R⁴ radicals are

[0105] and radicals having at least three carbon atoms are preferred andthe radicals

[0106] are particularly preferred.

[0107] n is preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.

[0108] The inventive ammonio-containing organosilicon compounds arepreferably prepared by reaction of (poly)amines with epoxy-containingorganosilicon compounds, especially by polyaddition.

[0109] The ammonio-containing organosilicon compounds obtained bypolyaddition are preferably prepared by

[0110] in a first stage reacting

[0111] (poly)amines (11) of the general formula

[0112] where R³, R⁴, n and x are each as defined above, withepoxy-containing organosilicon compounds (12) containing units of thegeneral formula

[0113] where R, R¹, a and b are each as defined above,

[0114] each E is the same or different and represents a monovalentSiC-attached organic radical which contains an epoxy group, and

[0115] c is 0 or 1,

[0116] with the proviso that the sum of a+b+c is ≦3 and that at leastone E radical is present per molecule,

[0117] with the proviso that the employed ratio of N-attached hydrogenin (poly)amine (11) to epoxy group in organosilicon compound (12) issuch that toluene-soluble amino-containing organosilicon compounds areobtained,

[0118] and in a second stage protonating

[0119] the amino-containing organosilicon compounds obtained in thefirst stage by addition of acids (14), preferably having a pK_(a) valueof greater than 0, more preferably of greater than 2 and most preferablyof greater than 3, partially or fully and preferably fully,

[0120] with the proviso that the ammonio-containing organosiliconcompounds obtained contain at least one moiety of two protonatednitrogen atoms joined together through at least three carbon atoms.

[0121] The amino-containing organosilicon compounds obtained in thefirst stage in the course of the polyaddition are soluble in toluene, ieare uncrosslinked, in contradistinction to toluene-insolubleorganosilicon compounds which are crosslinked. The organosiliconcompounds obtained are soluble in toluene in any proportion and arepreferably 100 percent by weight soluble in toluene at a temperature of25° C. and a pressure of about 1020 hPa on organosilicon compounds andtoluene being mixed in a ratio of 1:1 (parts by weight) and preferably1:10 (parts by weight).

[0122] The ammonio-containing organosilicon compounds obtained after thepolyaddition contain siloxane blocks which are joined together throughat least one di- or polyvalent ammonium radical.

[0123] Examples of (poly)amines (11) are primary amines of the generalformula R³—NH₂,

[0124] where R³ is a radical which is substituted by a nitrogen atom,such as

Me₂NC₃H₆NH₂

Et₂NC₃H₆NH₂

Me₂NC₄H₈NH₂

Me₂NC₂H₄NMeC₂H₄NH₂

Et₂NC₃H₆NEtC₃H₆NH₂

[0125] 4-amino-2,2,6,6-tetramethylpiperidine

[0126] and

[0127] 4-amino-1,2,2,6,6-pentamethylpiperidine,

[0128] and primary amines of the general formula R³—NH₂,

[0129] where R³ is a radical substituted by an oxygen atom and anitrogen atom, such as

Me₂NC₃H₆(C₂H₄O)_(s)C₃H₆NH₂

[0130] and

Et₂N(C₃H₆O)_(s)(C₂H₄O)_(s)C₃H₆NH₂,

[0131] where s is as defined above,

[0132] Me is methyl, Et is ethyl and Bu is n-butyl.

[0133] Further examples of (poly)amines (11) are propylenediamine,1,6-diaminohexane, dipropylenetriamine, isophoronediamine andneopentanediamine.

[0134] The E radicals preferably conform to the formula

[0135] where R⁵, R⁶, R⁷ and t are each as defined above.

[0136] The polyaddition is preferably carried out using epoxy-containingorganosilicon compounds (12) conforming to the general formula

E_(d)R_(3−d)SiO(SiR₂O)_(o)(SiREO)_(p)SiR_(3−d)E_(d)   (VIII),

[0137] where R and E are each as defined above,

[0138] d is 0 or 1, and especially 1,

[0139] o is 0 or an integer from 1 to 1 000 and especially from 5 to200, and

[0140] p is 0 or an integer from 1 to 10, preferably 0 or from 1 to 6and more preferably 0.

[0141] The viscosity of the epoxy-containing organosilicon compounds(12) is preferably in the range from 1 to 100 000 mPa.s at 25° C. andmore preferably in the range from 10 to 2 000 mPa.s at 25° C.

[0142] Examples of E radicals are

[0143] 3,4-epoxybutyl,

[0144] 5,6-epoxyhexyl,

[0145] 7,8-epoxyoctyl,

[0146] glycidoxyethyl,

[0147] glycidoxypropyl,

[0148] 2-(3,4-epoxycyclohexyl)ethyl,

[0149] 2-(3-epoxyphenyl)ethyl

[0150] and also epoxy itself,

[0151] of which glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl arepreferred and glycidoxypropyl is particularly preferred.

[0152] Processes for preparing epoxy-containing organosilicon compounds(12) are known to one skilled in the art.

[0153] Preferred embodiments are the epoxidation of aliphaticallyunsaturated organopolysiloxanes and the addition of terminallyunsaturated organic epoxy compounds, such as allyl glycidyl ether or4-vinylcyclohexene oxide, which is catalyzed by precious metal(compounds), to organopolysiloxanes containing silicon-attachedhydrogen.

[0154] The epoxy-containing organosilicon compounds (12) used in thepolyaddition preferably contain from 1 to 10 and especially from 1 to 6epoxy groups per molecule. A particularly preferred embodiment is theuse of α,ω-diepoxypolysiloxanes.

[0155] The polyaddition is preferably carried out using (poly)amines(11) containing from 2 to 10 nitrogen-attached hydrogen atoms andespecially containing from 2 to 6 nitrogen-attached hydrogen atoms. Thenumber of nitrogen atoms per molecule is initially not dependent thereonbut is preferably in the range from 2 to 4.

[0156] The polyaddition may optionally employ amines (13) having justone N—H group per molecule, since these act as chain stoppers and thusrender the polyaddition controllable.

[0157] Any amines (13) used preferably conform to the general formula

[0158] where R⁸ and R⁹ are the same or different and each represent amonovalent hydrocarbon radical having 1 to 60 carbon atoms per radicalwhich may be interrupted by one or more separate hetero atoms selectedfrom the group consisting of nitrogen and oxygen, or

[0159] R⁸ and R⁹ together represent a divalent hydrocarbon radicalhaving 4 to 10 carbon atoms.

[0160] Examples of amines (13) are dibutylamine, piperidine,diethanolamine, trimethylethylenediamine, bis(2-diethylaminoethyl)amineand bis(3-dimethylaminopropyl)amine.

[0161] Amines (13), when used, are preferably used in amounts from 5 to40% by weight, based on the total weight of the (poly)amines (11).

[0162] In the polyaddition, the ratio of (poly)amines (11) toepoxy-containing organosilicon compounds (12) is preferably in the rangefrom 1:1 to 10:1, more preferably in the range from 1:1 to 5:1 and mostpreferably in the range from 1:1 to 4:1.

[0163] In the polyaddition, the stoichiometry of the reaction depends onthe ratio of nitrogen-attached hydrogen in (11) to epoxy groups in (12)(N—H/epoxy). This N—H/epoxy ratio can be varied within wide limits,according to the nature of the ingredients and the target range for theviscosities of the inventive organosilicon compounds. But preferably theN—H/epoxy ratio is not less than ≧1 in order that all the epoxy groupscan react, subject to the condition that toluene-soluble, ieuncrosslinked, products are obtained. A person of ordinary skill in theart knows how to vary the N—H/epoxy ratio in the process of the presentinvention as a function of the N—H groups in (11) and epoxy groups in(12), i.e. the functionality of the reagents, for example experimentallyby carrying out tests, so that toluene-soluble products may be obtained.Since secondary reactions and also incomplete reaction sequences withconversions below 100% of theory play a part, a person of ordinary skillin the art knows that possible limits must be determined experimentallyif particularly viscous products are to be prepared.

[0164] The polyaddition is preferably carried out in the first stage attemperatures above 25° C., although there is detectable reaction even atthe normal, ambient temperature.

[0165] But temperatures above 60° C. are preferable, temperatures in therange from 80 to 180° C. are more preferable and temperatures between100 and 150° C. are most preferable in the interests of a rapid andcomplete reaction. The polyaddition is preferably carried out at thepressure of the ambient atmosphere, i.e. at about 1000 hPa, althoughparticularly in the case of volatile (poly)amines (11) an elevatedpressure is advantageous in order that losses of N—H functions throughevaporation and hence a change in the stoichiometry may be avoided.

[0166] The pK_(a) value of acids used in the preparation of theinventive ammonio-containing organosilicon compounds is preferablygreater than 0, more preferably greater than 2 and most preferablygreater than 3. Any kind of acid or various kinds of acid can be used.It is preferable to use water-soluble organic or inorganic acids.

[0167] Examples of acids are

[0168] monocarboxylic acids of the general formula R′—COOH (Xa) where R′is a hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atomsper radical, such as formic acid, acetic acid, propionic acid, butyricacid, pivalic acid, sorbic acid, benzoic acid, salicylic acid andtoluylic acid,

[0169] and dicarboxylic acids of the general formula HOOC—R⁵—COOH (Xb),

[0170] where R⁵ is as defined above, such as

[0171] succinic acid, maleic acid, adipic acid, malonic acid andphthalic acid, and the monocarboxylic acids are preferred.

[0172] Particular preference is given to formic acid, acetic acid andpropionic acid.

[0173] Further examples of acids are sulfonic acids of the generalformula

R′—SO₃H (Xc)

[0174] where R′ is as defined above, such as

[0175] methanesulfonic acid, butanesulfonic acid,trifluoromethanesulfonic acid and toluenesulfonic acid,

[0176] and also inorganic acids, such as hydrochloric acid, hydrobromicacid, sulfuric acid and phosphoric acid. The exclusive use of thesestrong acids is not preferable.

[0177] Examples of R′ hydrocarbon radicals are the hydrocarbon radicalsR.

[0178] Accordingly, the organosilicon compounds according to the presentinvention preferably contain the corresponding X⁻ anions of the acidsused. Preferably, X⁻ is an anion of a corresponding water-solubleorganic or inorganic acid. Examples of X⁻ anions are therefore R′—COO⁻(Xa′), ⁻OOC—R⁵—COO⁻ (Xb′) and R′—SO₃ ⁻ (Xc′),

[0179] where R′ and R⁵ are each as defined above.

[0180] When, thus, the amino-containing organosilicon compounds arereacted with, for example, acetic acid, the organosilicon compoundsaccording to the present invention will contain the acetate anionscorresponding to the protonated nitrogen atoms.

[0181] The acids are preferably used in amounts of from 0.1 to 2.0 gramequivalents and more preferably from 0.5 to 1.5 gram equivalents, eachnumerical value being based on the amine nitrogen of theamino-containing organosilicon compounds,

[0182] the amount of acid being determined in such a way that, permolecule, there is obtained at least one moiety of two protonatednitrogen atoms joined together through at least three carbon atoms.

[0183] When, thus, 1 kg of the amino-containing organosilicon compoundscontains 14 g of basic nitrogen, it is for example preferable to usefrom 6 to 120 g of acetic acid and more preferable to use from 30 to 90g of acetic acid. The use of from 6 to 60 g of acetic acid leads in thisexample to a partial protonation, i.e. not all the basic nitrogen atomsof the amino-containing organosilicon compounds are protonated. The useof 60 g of acetic acid or more provides fully protonated products, theexcess acid serving to regulate the pH of the inventiveammonio-containing organosilicon compounds. The pH of the inventiveorganosilicon compounds can be lowered still further by adding even moreacid. Mixtures of this type exhibit the characteristics of bufferedsystems.

[0184] It is preferable for all the basic nitrogen atoms in theinventive organosilicon compounds to be protonated, including anynitrogen atoms in the R³ radicals, so that there are obtained as

[0185] (a) structural unit Y of the formula (I) preferably those of theformula

[0186] or, written differently,

[0187] and, as optionally included

[0188] (d) structural unit Y′ of the formula (I′) preferably those ofthe formula

[0189] or, written differently,

[0190] where m is equal to the sum formed from n+1 and the total numberof any basic nitrogen atoms in the R³ radicals,

[0191] [i.e. at most m=n+1+(n+1)Σ(N atoms in R³)]

[0192] R², R³, R^(3′), R⁴ and X⁻ are each as defined above,

[0193] with the proviso that any basic nitrogen atoms present in R³ areprotonated.

[0194] The aqueous compositions according to the present inventioncontain organosilicon compound in an amount which is preferably in therange from 2 to 60% by weight and more preferably in the range from 2 to20% by weight.

[0195] The aqueous compositions according to the present invention canbe used in fields where ammoniosiloxanes have hitherto been used,chiefly as softeners for substrates such as fibers, textiles, hair; iepolymer-based natural or synthetic substrates.

[0196] The aqueous compositions according to the present invention maybe stabilized by including (4) water-miscible solvents, such asisopropanol, diethylene glycol monomethyl ether, diethylene glycolmonobutyl ether, dipropylene glycol or dipropylene glycol monomethylether.

[0197] These solvents can be added before or after the addition ofacids. But it is preferable to add such solvents before any dilutionwith water.

[0198] If desired, it is also possible to use (5) emulsifiers to preparethe aqueous compositions, in which case nonionic emulsifiers arepreferred.

[0199] The aqueous compositions according to the present invention havethe advantage that the inventive ammonio-containing organosiliconcompounds are preferentially soluble or self-dispersing in water andcontain a lower level of basic nitrogen than previous organosiliconcompounds. This holds especially in comparison with organosiliconcompounds which contain amino or ammonium groups in which two nitrogenatoms are exclusively spaced apart by one or two carbon atoms.

[0200] The present invention further provides a process for impregnatingorganic fibers with the aqueous compositions according to the presentinvention.

[0201] The inventive process for impregnating organic fibers can beapplied to any organic fiber in the form of filaments, yarns, webs,mats, strands, woven, loop-formingly knitted or loop-drawingly knittedtextiles that have hitherto been impregnable with organosiliconcompounds. Examples of fibers which are impregnable are fibers composedof keratin, especially wool, copolymers of vinyl acetate, cotton, rayon,hemp, natural silk, polypropylene, polyethylene, polyester,polyurethane, polyamide, cellulose and blends of at least two thereof.As is evident from the foregoing enumeration, the fibers can be ofnatural or synthetic origin. The textiles can be present in the form offabric webs or garments or parts of garments.

[0202] Application to the fibers to be impregnated can be effected inany of the extensively described methods useful for impregnating fibers,for example by dipping, coating, casting, spraying, including sprayingfrom an aerosol pack, rolling, padding or printing.

[0203] The aqueous compositions according to the present invention canfurther also be used in formulations such as creams, shaving foams,shampoos, washing lotions, soaps, deodorants or hairsprays.

[0204] A further emphasis is on the use for treating mineral materials,specifically for hydrophobicizing surfaces. Preference is here given tosilicatic surfaces, to which the organosilicon compounds according tothe present invention exhibit particularly good adhesion. The presentinvention accordingly provides a process for impregnating silicaticsurfaces, especially glass, ceramics and natural rock, with the aqueouscompositions according to the present invention.

[0205] The aqueous compositions according to the present invention canfurther be used for impregnating sheetlike organic plastics, such asvinyl acetate, polypropylene, polyethylene, polyester, polyurethane,polyamide and polycarbonate. The present invention accordingly providesa process for impregnating sheetlike organic plastics with the aqueouscompositions according to the present invention.

EXAMPLE 1

[0206] 197.8 g of an α,ω-bis(glycidyloxypropyl)polydimethylsiloxanehaving the average chain length Si-51 are mixed with 7.64 g ofbis(3-aminopropyl)amine, 206 g of diethylene glycol monobutyl ether and5.8 g of isopropanol. The thinly viscous mixture at 23 mm²/s (25° C.) isheated to 130° C., whereupon the viscosity increases dramatically to afinal value of 10 100 mm²/s (25° C.) after 60 minutes. After cooling to95° C., 11.5 g of acetic acid are stirred in. The solution contains 0.41equ. of amine nitrogen per kg in protonated form (corresponds to 0.57%by weight of protonated amine nitrogen).

[0207] 30 g of this solution are diluted with 70 g of water andspontaneously forms a pH-neutral, clear, aqueous formulation which isfurther thinnable in any desired proportion.

EXAMPLE 2

[0208] 250.0 g of the epoxysiloxane of example 1 are mixed with 10.66 gof 1,6-diaminohexane, 260.0 g of diethylene glycol monobutyl ether and7.5 g of isopropanol. After 2 hours at 130° C. the reaction mixturereaches a viscosity of 730 mm²/s (25° C.). As it cools, 12.1 g of aceticacid are metered in. The solution then contains, per g, 0.35 meq. ofprotonated amine nitrogen (corresponds to 0.49% by weight of protonatedamine nitrogen) and a pH of about 7.5. Further mixing with 2.3 times theamount of water provides a clear aqueous formulation.

EXAMPLE 3

[0209] 255.0 g of the epoxysiloxane of example 1 are mixed with 12.77 gof dimethylaminopropylamine and 7.5 g of isopropanol and heated to 120°C. without further solvent. After a total of 6 hours, the viscosity hasrisen only to about 6 times the value (356 mm²/s at 25° C.). The ¹H NMRspectrum of this sample shows an epoxy group conversion of more than 99%of the amount used. The reaction product is freed of volatiles at 120°C. under reduced pressure to leave a clear oil having a viscosity of 620mm²/s at 25° C.

[0210] 30 g of the basic aminosiloxane copolymer are mixed with 1.4 g ofacetic acid and 30 g of diethylene glycol monobutyl ether and dilutedwith water to a total weight of 200 g. The neutral aqueous formulationcontains, per kg, 106 meq. of protonated amine nitrogen (corresponds to0.15% by weight of protonated amine nitrogen). It does not become cloudyon further dilution.

EXAMPLE 4

[0211] A 250 ml three-neck flask equipped with stirrer, reflux condenserand thermometer is charged with 100.0 g of a polydimethylsiloxane havingtrimethylsilyl end groups and glycidyl ether propyl side groups andhaving a viscosity of 1 420 mm²/s at 25° C. and an epoxy content of0.307 mmol/g, 6.1 g of 3,3-iminobis(N,N-dimethylpropylamine) and 15.9 gof 1-butanol. The contents are refluxed at about 135° C. for 6 hourswith stirring. The slightly cloudy, weakly yellowish solution is heatedout in a rotary evaporator at 150° C. under a full vacuum andsubsequently filtered. The product obtained has an amine number of 0.91mmol/g (corresponds to 1.27% by weight of amine nitrogen) and is weaklyyellow and clear.

[0212] 15.0 g of this polymer are dissolved in the same amount ofdiethylene glycol monobutyl ether and are protonated with 0.90 g ofacetic acid. This mixture is diluted with water to 100 g by vigorousstirring. The aqueous solution obtained is clear and further dilutablewithout precipitation.

EXAMPLE 5

[0213] 54 g of a hydrolysate of3-aminopropyl-3-aminopropylmethyldimethoxysilane are dissolved with 1090g of a commercially available silicone oil having trimethylsiloxane endgroups and a viscosity of 1000 mm²/s at 25° C. using 0.35 g of KOH andequilibrated in 0.9 g of methanol at 135° C. After 5 hours, the mixtureis at equilibrium and the basic catalyst is neutralized with 0.45 g ofacetic acid. Removal of the volatile siloxane cycles at 120° C. underreduced pressure leaves 996 g of an aminosiloxane havingH₂N(CH₂)₃NH(CH₂)₃ groups.

[0214] 30 g of this oil are dissolved in the same amount of diethyleneglycol monobutyl ether and protonated with 1.2 g of acetic acid; wateris then added to 200 g. The aqueous formulation obtained is clear andcontains, per kg, 90 meq. of protonated amine nitrogen (corresponds to0.13% by weight of protonated amine nitrogen).

What is claimed is:
 1. Aqueous compositions containing (1)ammonio-containing organosilicon compounds which, per molecule, containat least one moiety of two protonated nitrogen atoms joined togetherthrough at least three carbon atoms, (2) acid anions whose correspondingacids have a pk_(a) value of greater than 0, (3) water, optionally (4)water-miscible solvents and optionally (5) emulsifiers.
 2. Aqueouscompositions as claimed in claim 1, characterized in that the (1)ammonio-containing organosilicon compounds contain per molecule at leastone moiety of the general formula

where z is an integer from 1 to
 20. 3. Aqueous compositions as claimedin claim 1 or 2, characterized in that they are homogeneous aqueoussolutions.
 4. Aqueous compositions as claimed in claim 1, 2 or 3,characterized in that the corresponding acids of the acid anions (2)they contain have a pk_(a) value of greater than
 2. 5. Aqueouscompositions as claimed in any of claims 1 to 4, characterized in thatthe ammonio-containing organosilicon compounds contain (a′) at least onesiloxane unit of the general formula

where each R is the same or different and represents a monovalentoptionally halogenated hydrocarbon radical having 1 to 18 carbon atomsper radical, each R¹ is the same or different and represents amonovalent hydrocarbon radical having 1 to 8 carbon atoms per radical, ais 0, 1, 2 or 3, b is 0, 1, 2 or 3, with the proviso that the sum of a+bis ≦2, Y is an organic radical of the general formula

where R² is a divalent organic radical, R³ is a hydrogen atom or amonovalent hydrocarbon radical having 1 to 60 carbon atoms per radicalwhich may be interrupted or substituted by one or more separate heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur andhalogen, R^(3′) has the meaning of R³, R⁴ is a divalent hydrocarbonradical having 1 to 10 carbon atoms per radical, n is 0 or an integerfrom 1 to 10, m is an integer from 2 to the total number of nitrogenatoms in (I), each x is the same or different and represents 0 or 1, X⁻is an acid anion whose corresponding acid has a pK_(a) value greaterthan 0, with the proviso that the structural unit of formula (I)contains at least one moiety of two protonated nitrogen atoms which arejoined together through at least three carbon atoms, and (b) at leastone siloxane unit of the general formula

where R, R¹, a and b are each as defined above, with the proviso thatthe sum of a+b is ≦3.
 6. Aqueous compositions as claimed in claim 5,characterized in that R^(3′) is a hydrogen atom.
 7. Aqueous compositionsas claimed in claim 5 or 6, characterized in that the ammonio-containingorganosilicon compounds contain (d′) at least one bridge unit of thegeneral formula

where R, R¹, a and b are each as defined in claim 5, with the provisothat the sum of a+b is ≦2, Y′ is an organic radical of the generalformula

where R², R³, R⁴, n, m, x and X⁻ are each as defined in claim 5, withthe proviso that the structural unit of the formula (I′) contains atleast one moiety of two protonated nitrogen atoms which are joinedtogether through at least three carbon atoms.
 8. Aqueous compositions asclaimed in claim 5, 6 or 7, characterized in that R⁴ is a radical of theformula —(CH₂)₃—.
 9. Aqueous compositions as claimed in any of claims 5to 8, characterized in that R² is an organic radical selected from thegroup consisting of (Si)—(R⁵)_(t)—CR⁶(OH)CR⁶ ₂—(N)   (VI),

and a divalent hydrocarbon radical having 1 to 10 carbon atoms perradical, where (Si)— is the bond to the silicon atom of the siloxaneunit of the formula (IV) or (V) as the case may be and —(N) is the bondto the nitrogen atom of the radical Y or Y′ of the formula (I) or (I′)as the case may be, R⁵ is a divalent hydrocarbon radical having 1 to 10carbon atoms per radical which may be substituted by an ether oxygenatom, R⁶ is a hydrogen atom or a monovalent hydrocarbon radical having 1to 10 carbon atoms per radical which may be substituted by an etheroxygen atom, R⁷ is a trivalent hydrocarbon radical having 3 to 12 carbonatoms per radical and t is 0 or
 1. 10. Aqueous compositions as claimedin any of claims 5 to 9, characterized in that all the basic nitrogenatoms in the ammonio-containing organosilicon compounds are protonatedand m is equal to the sum formed from n+1 and the total number of anybasic nitrogen atoms contained in the R³ radicals.
 11. A process forpreparing the aqueous compositions of claim 1, characterized in that itcomprises mixing (1) ammonio-containing organosilicon compounds which,per molecule, contain at least one moiety of two protonated nitrogenatoms joined together through at least three carbon atoms, (2) acidanions whose corresponding acids have a pk_(a) value of greater than 2,(3) water, optionally (4) water-miscible solvents and optionally (5)emulsifiers.
 12. A process for impregnating organic fibers with aqueouscompositions as claimed in any of claims 1 to
 10. 13. A process forimpregnating silicatic surfaces with aqueous compositions as claimed inany of claims 1 to
 10. 12. A process for impregnating sheetlike organicplastics with aqueous compositions as claimed in any of claims 1 to 10.